Heterocyclic quaternary ammonium pentachlorophenates



PatentedFeb. 13, 1951 HETEROCYCLIC QUATERNARY AMMONIUMPENTACI-[LOROPHENATES Sivert N. Glarum, Wyncote, Pa., and Alva L. Honk,San Luis Obispo, Calif., assignors to Riihm & Haas Company,Philadelphia, Pa., a corporation of Delaware No Drawing. ApplicationOctober 22, 1946, Serial No. 704,986

6 Claims.

1 This invention deals with quaternary ammonium compounds having as ananion a pentachlorophenate group. It further deals with methods wherebythese compounds may be pre pared. In particular, the present applicationis directed to quaternary ammonium pentachlorophenates having nitrogenin a heterocycle and is a continuation-in-part of our application SerialNo. 502.049, filed September 11, 1943.

We have found that certain of these quaternary ammoniumpentachlorophenates may be prepared by heating together a heterocyclicamine having a saturated ring which includes a tertiary nitrogen atomwith the methyl or a benzyl ether of pentachlorophenol, for example,illustrating the reaction with substituted morpholine,

wherein R is a methyl or a benzyl group, including such substitutedbenzyl groups as chlorobenzyl, nitrobenzyl, and methylbenzyl, and R isan aliphatic, alicyclic, or arylaliphatic group, such as methyl, ethyl,propyl, isopropyl, butyl, isobutyl, amyl, hexyl, octyl, decyl,undecenyl, dodecyl, cetyl, octadecyl, octadecenyl, butoxymethyl,butoxyethyl, butoxybutyl, benzyl, methylbenzyl, tert.-butylbenzyl,phenoxyethyl, chlorophenoxyethyl, nitrophenoxyethyl, naphthoxyethvl.phenoxyethoxyethyl, 1,1 3,3-tetramethylbutylphenoxyethoxyethyl,phenoxypropyl, phenoxypropoxypropyl, decylphenoxyethyl, cyclohexyl,methylcyclohexyl, acyloxyalkyl, including acetyloxyethyl,acetyloxypropyl, butyryloxyethyl, 4hexanoyloxyethyl, lauroyloxyethyl,stearoyloxyethyl, and the like. When the group R contains more than sixcarbon atoms, the resulting quaternary ammonium compounds exhibitcapillary actlvity.

By a preferred method, a tertiary amine of the formula I R! RI\/ whereinR and R" together form a divalent group which jointly with the nitrogenforms a R 'OCeCls at a temperature between about 80 C. and about 180 C.with or without an organic solvent under normal, reduced, or increasedpressure. The compound formed in the reaction may be purified bystripping oil? volatile material, by treating with an absorbent such ascharcoal, by crys" tallizing, or by following other conventionalpurification steps.

-While the above method constitutes a preferred one, quaternary ammoniumcompounds having a pcntachlorophenate anion may also be prepared bymetathesis between a quaternary ammonium salt of a strong acid, such aschloride, bromide, or sulfate, and a soluble salt of pentachlorophenol,such as sodium or potassium pentachloro phenate. The metathesis may takeplace in an aqueous system or in a system with an organic solvent andthe salts formed by metathesis separated.

Yet another method of preparation of quaternary ammoniumpentachlorophenates, although one of somewhat limited scope because oflack of availability of starting materials, is the direct reaction of aquaternary ammonium hydroxide and pentachlorophenol. I

By the above methods there may be obtained practically any type ofquaternary ammonium pentachlorophcnatc. These are all new compoundshaving valuable properties which make them useful as disinfectants,bactericides, fungicides, textie assistants, and finishing agents,wetting agents, emulsifiers, etc.

The reaction involved for preparing heterocyclic quaternary ammoniumcompounds through metathesis may be illustrated as follows, usingpiperidines as typical amines and sodium pentachlorophenate as a typicalsoluble salt of this phenol,

cmom Rmx R\': cmo ri; Naococh R-N cm N cm CHZCHI R CHgCfi9 R' omen,

cm NaX R l cmoi each The new compounds of the formula R N/ R" OCaClswherein R and R" form a heterocycle with the nitrogen and togetherrepresent a saturated divalent hydrocarbon or ether chain, are ofconsiderable interest. B. may be any of the groups indicated above inconnection with the firstmentioned method of synthesis and may also beallyl, methallyl, benzyl, or other monovalent aliphatic, alicyclic,heterocyclic, or arylaliphatic group. R may be not only the methyl orbenzyl group supplied by the pentachlorophenyl methyl or benzyl ethersbut also any of the allphatic or arylaliphatic groups which areintroduced by so-called alkylating agents during the formation of aquaternary ammonium salt prior to the step of metathesis with a solublesalt of pentachlorophenol. These agents include such compounds as methylbromide, methyl iodide, methyl sulfate, ethyl bromide, ethyl sulfate,benzyl chloride, alkylbenzyl halides such as butylbenzyl bromide,halobenzyl chloride or bromide, nitrobenzyl chloride, haloacetates,including methyl, ethyl, or butyl methyl formate, chloroacetone, allylbromide, methallyl bromide, alkoxymethyl halides, represented bybutoxymethyl chloride, octoxymethyl bromide, or dodecyloxymethylchloride, etc. These agents thus supply such groups as methyl, ethyl,benzyl, carbmethoxymethyi, carbethoxymethyl, 2-ketopropyl,, allyl,methallyl, alkoxymethyl, etc. The strong anion or anionic group suppliedby such agents is, of course, replaced by the pentachlorophenate groupduring metathesis, while the organic radical, usually an aliphatic orarylaliphatic group, remains attached to the nitrogen.

Thus, there may be obtained such quaternary ammonium compounds as:

Butyl methyl piperidinium pentachlorophenate Heptyl methyl morpholiniumpentachlorophenate Dodecyl methyl pyrrolidinium pentachlorophenate Cetylmethyl thiomorpholinium pentachlorophenate octadecyl benzyl morpholiniumpentachlorophenate Iso-octyl benzyl pyrrolidinium pentachloro phenateDodecyloxymethyl ethyl morpholinium pentachlorophenate Dodecyloxyethylmethyl morpholinium pentachlorophenate Dodecyloxypropyl benzylmorpholinium pentachlorophenate stearoyloxyethyl methyl morpholiniumpentachlorophenate Butyryloxyethyl benzyl morpholinium penta- Cyclohexyloctyl morpholinium pentachlorophenate thiomorpholinium a-chloroacetate,

The quaternary ammonium compounds of this invention are readily absorbedfrom their solutions by textile fibers, particularly by fibrouscellulosic materials, and are tenaciously retained thereby. Fibers sotreated resist attack by fungi and bacteria very effectively. Fabrics,whether woven, knitted, or felted, can be protected thereby againstrotting and tendering. When the compound used for treating fibrousproducts has more than six carbon atoms in the substituent R, thecompound is fairly well retained. Compositions containing /4 or more ofone of the compounds of this invention are particularly useful formildewproofing cotton fabrics such as canvas or Osnaburg, jute fabrics,fabrics of other cellulosic fibers, or other types of fibers, includingwool, which may be exposed to conditions favoring the growth of fungithereon.

This invention is illustrated by the following examples of thepreparation of quaternary ammonium salts having as an.anion apentachlorophenate group.

Example 1 Example 2 A mixture of 38 parts of dimethylaminoethyl stearateand 28 parts of pentachloroanisole was stirred at C. for twelve hours.Titration of the amine showed that reaction was 90% complete.

Example 3 A mixture of 35 parts of octadecyl dimethylamine and 36 partsof pentachlorophenylbenzyl ether was heated at C. for four hours. Theproduct crystallized on cooling. It is very slightly soluble in waterbut soluble in alcohol.

Example 4 The above compound was also prepared by the following method:Solutions were prepared by dissolving 212 parts of octadecyl dimethylbenzyl ammonium chloride in 1500 parts of water and adding thereto asolution of 144 parts'of sodium pentachlorophenate in 1500 parts ofwater. An oily precipitate formed which was separated and dried invacuo. The yield was 280 parts of solid product.

Example 5 A solution of octadecyl trimethyl ammonium pentachlorophenate(described above) was pre-v pentachlorophenate in 244 parts of water. A

thick paste'resulted which'could be diluted to clear aqueous solution.

Example 6 A solution was prepared by dissolving 66 parts ofpentachlorophenol in a mixture of 125 parts of a 2.0 normal solution ofdimethyl dibenzyl ammonium hydroxide. 285 parts of water, and 320 partsof ethanol. The resulting solution contained 15% quaternary ammoniumpentachlorophenate.

Example v7 A mixture of 142 parts of stearic acid, 73 parts ofmorpholinoethanol, and eighty parts of toluene was stirred and refluxedwith a device for removing water from the condensed vapors. After eightparts of water had been removed, the toluene was distilled off undervacuum, leaving 212 parts of. solid residue which by titration contained5% stearic acid, the remainder being stearoyloxyethyl morpholine.

Eighty-three and six-tenths parts of the stemoyloxyethyl morpholine, 25parts of ethanol, and

this layer had C Hr C H2 C "H150 O O CrH4-N C 11.46,

CaCls Example 8 A mixture of 280 parts of octadecylamine, 375 parts ofethanol, 110 parts of sodium carbonate, and 143 parts offi-B'-dichlorodiethyl ether was stirred and refluxed for eight hours.The ethanol was removed by distillation and the product was washed withwater. It was distilled under vacuum and a fraction was collected at166-.193 C./4 mm. This fraction corresponded in composition to octadecylmorpholine. It had an apparent molecular weight of 347 by titration withstandard acid, compared with a theoretical weight of 339 for octadecylmorpholine.

Ninety parts of the above amine was mixed with fifty parts ofisopropanol and 38 parts of methyl iodide. and the mixture was stirredfor two hours at 80 C. After the isopropanol had been distilled offunder reduced pressure, a syrup remained which was completely soluble inwater.

Seventy-seven parts of the octadecyl morpholinium iodide thus preparedwas dissolved in 142 parts of water and 31.2 parts of sodiumpentachlorophenate was added. The mixture was warmed to 90 C. and aheavy liquid layer separated which contained 40% solids. The residueobtained from this layer had the composition:

Cunt! CHI-0':

0 Cur-CH:

CaC l The preferred compounds of this invention are thosechlorophenates'in which there occurs one N-substituentof twelve .toeighteen carbon atoms in an aliphatic hydrocarbon group, These compoundsin one or two per cent solutions are especially effective in preventinggrowth of molds and are well retained on fabrics under conditions whereleaching may occur.

In general, the compounds of this invention are soluble in water or inmixtures of water and an organic solvent miscible therewith, such asalcohol or acetone. Many compounds are also soluble in organic solventsthemselves, such as naphtha, benzene, alcohol, acetone, or the like.

The compounds are conveniently applied to fabrics from solutions,particularly aqueous solutions. therefrom, the fabrics are dried.Fabrics treated in this way are highly resistant to mildewing andtendering under conditions of severe expo sure. In confirmation of this,there are here presented results of mildew tests with a variety ofcompounds falling within the above general formula.

The tests were made under carefully controlled conditions and weredesigned to show not only growth or lack of growth of specific fungi butalso the effect on the cloth itself. In general, the

test methods used followed those prescribed in Tentative Specificationsof the Corps of Engineers, United States Army, T-1452, as amended I June10, 1941, and January 12, 1942.

A small strip of treated cloth was sterilized under fifteen pounds steampressure and placed in a test tube containing sterile agar with nutrientsalts. The agar was then inoculated with one-half to three-quarters of amilliliter of a suspension of spores of a selected fungus. The tube wasstoppered with a cotton plug and placed in an incubator maintained at 90F. for a week. Observations were then made as to growth or lack ofgrowth. In many cases, the tensile stren th of the strip was determined.

The tests were compared against control strips. Strips of the originalfabric, but untreated with mildewproofing agent, were tested along withstrips of treated fabric to make sure that copious growth of fungioccurred. Also, blank strips were given all of the handling and passedthrough all of the procedural steps except that these strips were notinoculated with spores in order to determine what eifect the procedureitself and the chemical agents might have. Another set of tests was alsomade with strips which were leached in a stream of tap water fortwenty-four hours. These were squeezed, sterilized, and tested by theprocedure described above.

glutinosum, Circular No. 737, S D. A., September, 1945, page 2.

After excess solution has been removed I results wererepeated in each ofthe following tests.

B. A 1% solution oi.

csuncmncm)ocgmocm. cu.

NOCsC-ls ColisCHg CH3 in denatured alcohol was applied to both Osnaburgand 48 x 48 sheeting. The cloth was squeezed to leave about a 100%take-up and dried. Strips of the two types of cloth were tested as abovewith Metarrhizium. No growth whatsoever occurred on unleached specimens,and the tensile strength of these strips was fully retained. The

leached strips. however, permitted some growth.

The compound used here has considerable solubility, and it should alsobe noted that leachi'astness was generally not so good for cloth treatedfrom solvent solutions as from water.

Controls treated with denatured alcohol without quaternary compound anddried supported a vigorous growth when inoculated and lost all breakingstrength. Controls not inoculated retain essentially their originalstrength.

C. The compound Giulia CH:

0.015 CoHsCH: CH;

was tested at two levels of concentration, 1% and 2%, in alcoholicsolutions. No growth occurred on strips of unleached Osnaburg withMetarrhizium sp., Chaetomium globosum, or Aspergillus niger. A trace ofgrowth was noted on leached strips with Aspergillus niger andChaetomium, but the tensile strength was little changed. Tests with 48 x48 cotton sheeting in general confirmed tze findings with Osnaburg,although there was an increased tendency for leaching of agent to ccc rwith this fabric and a concomitant tendency for the fabric to beattacked.

D. The compound C12H25(CH3)3NOC6C15 was applied from a 1% solution inalcohol. Strips or both Osnaburg and sheeting were tested againstMetarrhizium sp., and such compound was found to prevent the growth offungus thereon. These strips retained atleast 90% of their strengthduring the test.

E. A 1% aqueous solution of CeHsCHz (CH3) sNOCtCls 8 and one part ofalcohol. This was applied to both Osnaburg and sheeting in the usualway. Unleached strips were completely resistant to the growth ofMetarrhizium sp. Leached strips of impregnated Osnaburg, whilepermitting a rather copious growth, retained at least of their tensilestrength.

G. A 1% solution of cu,- -cn-cu, cm

in alcohol was applied to both Osnaburg and 48 x 48 cotton sheeting, theexcess solution removed to leave take-up of solution, and theimpregnated cloths dried. No growth of Metarrhizium sp. was observed ontest strips and at least 90% of the tensile strength was retained bythese test strips. Some growth occurred on leached strips with the samefungus with concomitant partial loss of strength.

H. A 1% solution of in alcohol was used as in the previous example.Neither leached nor unleached strips of 48 x 48 cotton sheetingsupported an growth of Metarrhizium sp. There was no growth on unleachedOsnaburg, but slight growth on leached Osnaburg.

I. Tests on wool suiting were made with a product prepared by metathesisfrom equal parts by weight of p-tert.-octyl-phenoxyethoxyethyl dimethylbenzyl ammonium chloride, sodium pentachlorophenate, and alcohol. Asolution of 1.5% of the crude reaction product was made in water andapplied to the suiting, which was then squeezed to a 100% take-up, anddried.

Against Metarrhizium sp. unleached pieces permitted but a trace ofgrowth and leached pieces but slight growth while, on control samples, acopious growth occurred. These results were duplicated with Chaetomium.globosum.

J. A 1% dispersion of the compound obtained in Example 7 was applied toStrips of Osnaburg and muslin fabrics and tested as above with bothMetarrhizium and Chaetomium. No growth occurred on leached or unleachedstrips and there was little, if any, change in tensile strength.

K. A 1% dispersion of the product prepared in Example 8 was applied tostrips of Osnaburg and muslin fabric which were tested againstMetarrhizium. There was no visible growth on any of the strips, whetherunleached or leached. Other strips were tested against Aspergz'llusniger. There was no evident growth on the Osnaburg strips, whetherleached or unleached, nor growth on unleached muslin strips.

The new quaternary ammonium pentachlorophenates are highly effectivemildew resisting compounds for use on textile fibers. They are superiorto the quaternary ammonium salts of strong acids and topentachlorophenol or its alkali salts, particularly in that the newcompounds rcsist leaching and are effective where other organiccompounds fail. Their capacity to combat growth on nitrogenous fibers isunusual and of con iderable value.

7 A 1% solution of the long-chained quaternary wherein R is a member ofthe class consisting of monovalent aliphatic hydrocarbon radicals of notover eighteen carbon atoms and beta-alkanoyloxyethyl groups in which thealkanoyl group contains not over eighteen carbon atoms, R and R"together form a saturated divalent group which forms a heterocycle withthe nitrogen and which is a member of the class consisting ofvCH2CHzCH2CH2-, CH2CH2CH2CH2CH2, CH2CH2OCH2CH2-, and -CH2CH2SCH2CH2, andR' is a member of the class consisting of methyl and benzyl groups.

2. As a new chemical compound,

CH3 011,011, 0,133.00 oc2H4i O CflC15 CH1Cg 3. As a new chemicalcompound,

CH; CHzCHn Cis ar- O CaCl CH5CI b 10 4. Quaternary ammoniumpentachlorophenates of the formula CHaCH: CH: 0 N-R CHaC: 0 00015wherein R is an alkyl group of seven to eighteen carbon atoms. 5.Quaternary ammonium pentachlorophenate of the formula 011,011, CH2C0H5N-R CHzCQn OCoCI wherein R is an alkyl group of seven to eighteen carbonatoms.

.6. Quaternary ammonium pentachlorophenates of the formula CHzC z CH:

N-n cmcfil o 0001, wherein R is a beta-alkanoyloxyethyl group' in whichthe alkanoyl group contains not over eighteen carbon atoms.

SIVERT N. GLARUM.

ALVA L. HOUK.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,127,103 Bruson Aug. 16, 19382,191,922 Bruson Feb. 2'7, 1940 2,268,395 Henke et a1. Dec. 30, 19412,295,504 Shelton Sept. 8, 1942

1. QUATERNARY AMMONIUM PENTACHLOROPHENATES OF THE FORMULA